CA1203939A - Staged copolymerization of polyesters - Google Patents

Staged copolymerization of polyesters

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Publication number
CA1203939A
CA1203939A CA000443207A CA443207A CA1203939A CA 1203939 A CA1203939 A CA 1203939A CA 000443207 A CA000443207 A CA 000443207A CA 443207 A CA443207 A CA 443207A CA 1203939 A CA1203939 A CA 1203939A
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Prior art keywords
stage
acid
polyester
segment
moles
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CA000443207A
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French (fr)
Inventor
Eugene G. Sommerfeld
Andrew P. Stamegna
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EI Du Pont de Nemours and Co
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EI Du Pont de Nemours and Co
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Priority to US06/450,135 priority Critical patent/US4442269A/en
Priority to US450,135 priority
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/78Preparation processes
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08GMACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • CCHEMISTRY; METALLURGY
    • C09DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09DCOATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D167/00Coating compositions based on polyesters obtained by reactions forming a carboxylic ester link in the main chain; Coating compositions based on derivatives of such polymers

Abstract

TITLE
Staged Copolymerization of Polyesters ABSTRACT

Polyester copolymers prepared by a non equilibrium, two-stage process conducted without external catalysts have relatively high polydispersity and low viscosity, permitting the preparation of high solids paints.

Description

, TITLE
Staged Copolymeriza-tion of Polyesters BACKGROUND
-The present invention concerns a polymeri-zation process for producing branched polyesterswith characteris-tics especially useful in high solids paints.
Environmental and economic concerns often make it desirable to minimize the quantity of organic solvent released to the atmosphere in the application of paints, such as to automobiles, either in single color coats or in color coat/clear coat or other applications. One way to do this is to make a paint with higher solids content which contains less solvent to evaporate.
Several properties must be balanced and reconciled in developing such a paint. Higher polydispersity polymers sometimes permit the preparation of higher solids paints, but it is necessary to keep the viscosity, rheology and other properties of the paint under control. Polydispersity is defined as the ratio of the weight average molecular weight, Mw, to the number average molecular weight, Mn. Polymers having higher Mw ~5 often make paints with higher viscosity unless the polydispersity is also high. Such high viscosities , can make it more difficult to apply the paint by conventional technlques such as spraying.
It would be desirable to have polymers which can be used to make paints with relatively high solids content and low viscosity.

3~33~

SUMMARY OF THE INVENTION
The present invention provides a non-equilibrium, two stage polymerization process conducted without external catalysts for producing polyester copolymers having a linear segment with terminal hydroxyl groups and a number average molecular weight (Mn) of at least about 500 and a branched segment with lateral hydroxyl groups wherein, in the first stage of the process, one half of the carbo~l groups of a diacid or a diacid anhydride axe reacted in approximately stoichiometric proportions with one of (A) one half of the hydroxyl groups of the linear segment and (B) 10-80% of the hydroxyl groups of the branched segment to form a first reaction product, and then,in the second stage of the procass, the other half of the carboxyl groups of the first reaction produc-t are reacted in approximately stoichiometric proportions with the hydroxyl group of the other of (A) and (B).
Preferably, after the first stage but before the second stage of polymerization the branched segment has a number average molecular weight of 750-1000, a hydroxyl number of 175-300, an acid number of 20-60 if the carboxyl group has been reacted first with the branched segment or less than 5 if the carboxyl group has been reacted first with the linear segment, and a number average functionality of 2.5-11; and the linear segment has a number average molecular weight of 500 3000, a hydroxyl number of 15-300, an acid number of less than 5 or 20-60, respectlvely, and a number average functionality of 1.1-2.

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The first stage reaction is preferably conducted at at least 100C, more preferably at at least 150C. The second stage reaction is preferably conducted at at least 200C.
The polyester copolymers themselves and coating compositions comprising such copolymers and melamine/formaldehyde, di- or poly-isocyanate, or urea/formaldehyde crosslinkers are also part of the invention.
DETAILED DESCRIPTION
In contrast to single-stage batch or continuous polymerization processes or externally catalyzed polymerization processes, the present invention provides a means for producing specific polymer architecture in structured branched co-polyesters, permitting obtaining high poly-dispersity and high solids paints with viscosity low enough for practical application such as by spraying.
In one embodiment of the invention, in a first stage reaction a diacid anhydride is reacted with lateral hydroxyl groups of a branched polyester prepolymer or oligoester, referred to hereafter as a branched segment. The proportions are such that about one half of the carboxyl groups in the diacid anhydride react with about 10 to 80~, preferably about 25~ of the hydroxyl groups in the branched segment.
Then in a second stage reaction a linear polyester prepo'ymer, oligoester or segment with terminal hydroxyl groups is reacted with the reaction product of the first stage reaction.
The proportions are such that the hydroxyl groups on one en of the linear segments (or one half of the total hydroxyl yroups on the linear segments) react with the remaining carboxyl groups on the diacid anhydrides in the reaction product of the first stage reaction. These reactions are endothermic condensation polymerizations which can be terminated by cooling. The progress of the reactions can be followed or determined by measuring the acid number.
If external polymerization catalysts, such as dibutyl tin oxide, otherwise known as exogenous catalysts, were present during either or both stages, or if both reactions were conducted in a single stage, the resulting polymer would be quite different, having a scrambled molecular weight, lower polydispersity, and less desirable properties for making high solids paints. This has been demonstrated experimentally. While it can be said that the present polymerization reactions are somewhat autocatalytic, with one of the reactants acting as a catalyst wh-ich is consumed in the reaction, thereby quenching or killing the catalytic action when the reactant is consumed, this is quite a different phenomena than external or exogenous catalysis, excluded by the present invention, wherein catalytic effects continue until equilibrium results are achieved with their characteristic less desirable broad molecular 3~ weight distributions and other effects. Among the undesirable effects of reaction to equilibrium would be increased transesterification, scrambling ~Z~3g~39 of the polymer structure, and premature cross-linking leading toward gellation and unusable product. Indeed, while not desiring to be committed to any particular hypothesis, it appears that the present invention creates a kinetically controlled polymerization that can be stopped before reaching equilibrium, thereby giving a more desirable product. In contrast, the equilibrium product of a catalyzed or single stage reaction is thermo-dynamically determined, has a less specific polymerarchitecture, and is less desirable for certain purposes.
Among other uses, copolyesters of the present invention are particularly useful as the binder in a color coat over both rigid and flexible substrates in automobiles, to be covered with a clear coat finish to add aesthetic appeal.
The linear segments preferably can be provided by the following monomers:
neopentyl glycol 1,6-hexanediol Esterdiol-204, a commercial diol produced by Union Carbide o-phthali~ anhydride isophthalic acid adipic acid a~elaic acid The branched segments preferably can be provided by the following monomers:
neopentyl glycol hexanediol trimethylolpropane o-phthalic anhydride , 33~

isophthalic ac:id adipic acid aæelaic acid Preferably the linear and branched segments are S linked together through the following capping agents:
o-phthalic anhydride succinic anhydride glutaric anhydr.ide The nature of the invention will now be further demonstrated by the following examples in which percentages and proportions are given by weight except for ratios which are molar and except as indicated otherwise.
In the examples, the molar ratios of constituent groups in the oligoesters and the acids or their anhydride equivalents are given in the following terms:
: diol/triol = X1 polyol/diacid = X2 aromatic diacid/aliphatic diacid =-X3 diol/diacid = X4 The monomers used include the following:

neopentyl glycol OH-CH2-C-CH2-OI~

: 1,6-hexanediol HO-C~2~CH2-CH2-cH2-c~2-cH2 :

o-phthalic anhydride o 3~3~33 isophthalic acid adipic acid H02C-(C~I2)4-cO2 azelaic acid H02C-(CH2)7-cO2 trimethylolpropane HOCH2-C-CH2-OH

succinic anhydride giutaric anhydride The following Table of Contents can aid in understanding the examples.
TABLE OF CONTENTS
Ex. Subject and Purpose 1 Branched Oligoester 1 Used as prepolymer for staged polyesters used in flexible color coats and clear coats.
20 2 Linear Oligoester 1 Used as prepolymer in com-bination with branched oligoester 1 for same end uses.
3 Staged Polyester Lo Lcw molecular weight/high acid number staged polyester.
Prepared by ~~ombination of branched oligoester 1 and linear oligoester 1 via o-phthalic anhydride (mole ratio = 1:1:1). Used in flexible color coat and clear coat.

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Ex. urpose 4 Staged Polyester lB High molecular weight/low acid number staged polyester. Used and prepared as in lo.
Branched Oligoester 2 Used as prepolymer in studies done in staged addition.
6 Linear Oligoester 2 Lower (or medium molecular weight) linear esterdiol.
Used in staged polyesteri-fication with branched oligoester 2 to note the effect of lowering molecular weight of linear segment on properties of staged polymers.
7 Staged Polyester 2A Using succinic ar~lydride.
8 Staged Polyester 2B Using glut æ ic anhydride.
9 Branched Oligoester 3 Used as prepolymer in studies done in staged addition.
Tinear Oligoester 3 11 Staged Polyester 3A Using carboxylated branched segment.
25 12 Staged Polyester 3B Using carboxylated linear segment.
Gcmp æ . Batch Control experiment in con-Tests Polymerization junction with 3A and 3B.
moating Variations Varying compositions in color coat.
Varying ccm~ositions in clear cost.

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Ex. Subjec_ and Purpose Color Coat/Clear Coat Formulations 13 Flexible polyester color coat.
5 14 Flexible polyester clear coat.
Rigid polyester cleax coat.
Application 16 Flexible polyester color coat/flexible polyester clear coat.
17 Flexible polyester color coat/rigid polyester clear coat.

15 Example 1 This is an example of the preparationof a branched segment in which the chemicalcomposition has been balanced so as to provide an optimum hardness/flexibility balance in tub-sequent coating compositions. This segment will be co-condensed with the linear segment described in Example 2 to provide subsequent staged co-polyesters. The copolymerizations of these two segments will be described in Examples 3 and 4.
Xl = 1.17
2 = 1.3 X3 = 0.33 To a 12-liter flask equipped with a mechanical stirrer, electric heating mantle, nitrogen inlet tube, packed column, Dean-Stark water separator, batch and vapor thermometers and water cooled condenser are charged the following ingredients:

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2184 g neopentyl glycol (21 moles) 2430 g trimethylol propane (18 moles) 1245 g isophthalic acid (7.5 moles) 4230 g azelaic acid (22.5 moles) The mixture is hea-ted to distilling at temperatures of 140C -to 260C until 1080 g (60 moles) of water are collected. The resultant branched oligomer has the following physical constants:
Acid no. = 1.35 mg KOH at 100% wt solids Theoretical hydroxyl no. = 224 mg KO~ at 100~ wt solids Measured hydroxyl no. = 228 mg KOH
Mn = 1000 (vapor phase osmometry) Theoretical Mn = 1001 GPC (gel permeation chromatography) molecular weight distribution:
number average Mn = 1600 weight average Mw = 6200 Z average Mz = 18,000 polydispersity d = 3.88 Eirst order glass transition temperature (Tg) =
-39C (differential scanning colorimetry) example 2 This linear segment was prepared with a chemical composition and molecular weight to pro-vide the optimum balance of solution properties and physical properties in the staged polyesters of Examples 3 and 4.
To a 12-liter flask equipped as in Example 1 are added the following ingredients:

., .

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3993.60 g neopentyl glycol (38.4 moles) 1135 g 1,6-hexanediol (9.6 moles) 1494 g isophthalic acid (9 moles) 3948 g azelaic acid (21 moles) The mixture is heated to distilling at temperatures of 145C-265C until 1080 g (60 moles) of watex are collected. The resultant linear oligoester has the following physical properties:
Acid no. = 1.25 mg KOH of 100% wt solids Theoretical OH no. = 213 KOH at 100% wt solids Measured OH no. = 210 mg KOH
Theoretical Mn = 528 Mn vapor phase osmometry) = 540 GPC molecular weight distribution:
Mn = 725 Mw = 1300 Mz = 2300 d = 1.79 Tg = -52C
Example 3 STAGED POLYESTER lA
..
This copolyester is the product of the co-condensation of the polymers from Examples 1 and 2. The polymer is prepared by initial car-boxylation of the branched segment with o-phthalic anhydride. The stoichiometry of this step is such that 25% of the available hydroxyl grQups of the branched segment are converted to carboxyl groups vla the ring opening reaction with the anhydride. The mole ratio of the components is 1 mole branched segment/l mole phthalic anhydride.

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The next step is the co-condensation of this intermediate with the linear oligomer from Example 2. The final stoichiometry of total reaction is 1/1/1 (branched segment/anhydride/linear segment).
The condensation is carried out to an acid number value between 10-15 mg KOH at 100~ weight solids.
To a 12-liter flask equipped as in previous examples are added 4800 g ~4.8 moles) of branched oligomer 1, 711 g (4.8 moles o-phthalic anhydride and 160 g of xylene. The mixture is heated at 125C-150C for 1 hour. There should be no water removal at this stage. Then 2535 g (4.8 moles) of linear oligoester 1 are added and the entire mixture is heated to distill 15 60-65 g of water (approx. 3.5 moles) at temperatures of 220-250C. The resin is diluted with 1250 g of methyl ethyl ketone (MEK). The physical - properties of the resulting structured copolyester are as follows:
Acid no. = 10-15 mg XOH at 100~ weight solids Theoretical OH no. = 145 mg KOH at 100%
weight solids Measured OH no. = 143 mg KOH
Wt % solids = 85 Gardner-Holdt viscosity = Z to Z2 at 25C
GPC molecular weight distribution:
Mn = 1600 Mw = 9500 Mz = 32,000 30 d = 5.94 Tg = -32C
:

~3~139 This polymer can then be blended with melamine and with various amounts of the polymer in Example 4 to provide flexible metallic color coats and/or hard and flexible clear enamels.
Example 4 STAGED POLYESTER lB
This polymer is prepared in the same manner as Example 3 except that the polymeri-zation in the last stage is carried out to an acid number of less than 5. This polymer is higher in molecular weight and provides more flexible films than s-taged polyester lA. If the same quantities of Example 3 are used, then at least 8604 g (4.8 moles) of water must be collected to achieve the desired acid #. The polymer exhibits the following properties:
Acid no. = 1 to 5 mg KOH at 100% wt solids Theoretical OH no. = 135 mg KOH at 100%
wt solids Measured OH no. = 132 mg KOH
Wt % solids = 85 Gardner-Holdt viscosity = Z2 to Z3 at 25C
GPC molecular weight distributiono Mn =2100 Mw =16,000 Mz =68,300 d = 7.62 Tg = -34C
Example 5 The branched oligomer described in this example is co-condensed with the linear oligomer of Example 6 in the manner described in Example 4. Thls branched segment has been made more flexible by the introduction of 1~6-hexanediol as a flexible monomer.
Xl = 1.17 X2 = 1.3 X3 = 0.67 To a 5-liter flask equipped as in previous examples are added:
488.4 g neopentyl glycol (4.69 moles) 554.17 g 1,6-hexanediol (4.69 moles) 1086.8 g trimPthylolpropane (8.05 moles) 1513.4 g azelaic acid (8.05 moles) 891 g isophthalic acid (5.37 moles) The entire mixture is heated to distill 483 g (26.84 moles) of water at temperatures of 150C-270C. The resultant oligoester has the following physical constants: -Acid no. = 0-5 mg KOH at 100% wt solids Theoretical OH no. = 223 KOH at 100~ wt solids I: Measured OH no. = 220 mg KOH
: Theoretical Mn = 1006 Mn (vapor phase osmometry) = 1000 ::: 25 GPC molecular weight distribution:
: Mn =1200 : Mw =5940 Mz =19,800 : d = 4.93 Tg = -33C
I:
: :
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39~39 Example 6 ,. _ This linear oligoester is prepared at higher molecular weight than the oligomer des-cribed in Example 2. The purpose of this preparation is to allow for a more flexible and harder linear segment in subsequent staged polymer of Examples 7 and 8.
X3 = 0.67 X4 - 1.3 To a 5-liter flask equipped as before are added:
1123.2 g neopentyl glycol (10.8 moles) 566.4 g 1,6-hexanediol (4.8 moles) 796.8 g isophthalic acid (4.8 moles) 1353.6 g azelaic acid (7.2 moles) The mixture is heated to distill 432 g ~24 moles) of water at temperatures of 150C-270~C. -The resultant linear oligoester has the following physical constants:
Acid no. = 0-5 mg KOH at 100% wt solids ; Theoretical OH no. = 118 mg KOH at 100% wt solids Measured OH no. = 116 mg KOH
Theoretical Mn - 950 Mn vapor phase osmometry) = 980 GPC molecular weight distribution:
Mn = 1100 Mw = 2170 30 My = 3700 d = 1.97 Tg = -41C

,, )3~3~9 Example 7 STAGED POLYESTER_2A USING SUCCINIC ANHYDRIDE
This polymer was prepared in such a way as to provide a stoichiometry balance of 1 mole branched segment Example 5/1 mole succinic anhydride/l mole linear segment of Example 6.
Again this stoichiometric balance allows for reaction of 25~ of the available hydroxyl functionality of the branched segment with anhydride followed by extension with the linear segment. This polymer provides fairly hard and very flexible pigmented and clear enamels when crosslinked with melamines.
To a 5-liter flask equipped as before are added 1500 g (1.49 moles) of branched oligoester 2 of Example 5, (1.49 moles) of succinic anhydride and 61 g of xylene. The mixture is heated at 125C-150C for 1 hour and then 1411 g (1.49 moles) of linear oligoester 2 are added. The entire mixture is heated to distill 27 g (1.49 moles) of water at 210C-260C.
The resin is diluted with 475 g of MEK to yield a polyester having the following physical properties:
Acid no. = 0-5 mg KOH at 100% wt solids Theoretical OH no. = 110 mg KOH at 100 wt solids Measured OH no. = 92 mg KOH
weight solids = 85 Gaxdner-Holdt viscosity = Z4 at 25C
GPC molecular weight distribution:
Mn = Z600 Mw = 23,000 Mz = 108,000 d = 8.85 Tg = -36C
Example 8 ____ The succinic anhydride in the previous example is replaced by 170 g (1.49 moles) of glutaric anhydride. This anhydride leads to lower viscosity resins than succinic anhydride without affecting the film properties of -the subsequent enamels. As a result of this, glutaric anhydride may be a preferred capping agent over succinic and o-phthalic anhydride for certain end uses.
Acid no. = 0-5 mg KOH at 100~ wt solids Theoretical OH no. = 109 mg KOH at 100%
wt solids Measured OH no. = 108 % weight solids = 85 Gardner-Holdt viscosity = Z2 at 25C
GPC molecular weight distribution: -Mn = 2500 Mw = 21,000 Mz = 71,000 d = 8.40 Tg = -~0C
The following examples serve to illustrate the effect of staging the polyesterirication vs.
using a batch or continuous polymerization. The polymers described herein may or may not be used in coatings formulations, however, the theoretical aspects of staged polyesterification will be illustrated.
3~3~

Example 9 Xl = 1.17 X2 = 1.3 ~3 = 1.0 To a 5~1iter flask equipped as before are added the following ingredients:
725 g neopentyl glycol (7 moles) 810 g trimethylolpropane (6 moles) 830 g isophthalic acid (5 moles) 940 g azelaic acid (5 moles) The mixture is heated to distill 360 g (20 moles) of water at temperatures of 160C-250C.
The resultant oligoester has the following physical constants:
Acid no. = 0-5 mg KOH at 100% wt solids Theoretical OH no. = 228 mg ~KOH at 100%
wt solids Measured OH no. = 226 20 Theoretical Mn - 983 Mn (vapor phase osmometry) = 950 GPC molecular weight distribution:
Mn = 1300 ~Iw = 8000 Mz = 32,000 d = 6.15 Tg = -13C
This branched oligomer is then coy condensed with the linear segment prepared in the next example according to the procedures of Examples 11 and I2.

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Example 10 ._ X4 = 1.2 To a 5-liter flask equipped as before are added the following ingredients:
1622.4 g neopentyl glycol (15.6 moles) 2444 g azelaic acid (13 moles) The mixture is heated to distill 468 g (26 moles) of water at temperatures of 1S5C-260C.
The resultant linear oligoester has the following physical constants Acid no. = 0-5 Theoretical OH no. = 81 Measured OH no. = 86 Theoretical Mn = 1385 Mn (vapor phase osmometry) = 1300 GPC molecular weight distribution:
Mn = 1500 Mw = 3100 -I Mz = 5200 d = 2.07 ; Tg = -52C
xample 11 --This polymer is prepared by first reacting 25~ of the hydroxyl groups of branched oligoester 3 of Example 9 with o-phthalic anhydride to affect 25~ carboxylation of the branched segment. The linear oligoester 3 of Example 10 is then added and the copolymerization is carried out. The stoichiometry of the reaction is 1 mole~branched segment/l mole 2-phthalic anhydride/l mole linear segment.

.

a ~g To a 5-liter flask equipped as in previous examples are added 737 g (0.75 moles) of branched oligoester 3, 111.4 g (0175 moles) of _-phthalic anhydride and 17 g of xylene. The mixture is heated at 125C-150C for 1 hour and then 1038 g (0.75 moles) of linear oligomer 3 are added. The entire mixture is then heated to distill 13.5 g (0.75 moles) of water at 220C-270C.
The resin is then diluted with 314 g of xylene to provide a polyester resin with the following physical properties:
Acid no. = 0.50 Theoretical OH no. = 90 Measured OH no. = 88 % weight solids = 85 Gardner-Holdt viscosity = Z7 at 25C
GPC molecular weight distribution.
Mn = 2700 Mw = 110,000 Mz = 933,000 d = 40.7 Tg = -34C
Example 12 `STAGED POLYESTER 3B CARBOXYLATED LINEAR SEGMENT
This example describes the reversal of steps used in Example 11. The linear oligoester 3 of Example 10 is first carboxylated with o-phthalic anhydride to an extent of 50% carboxylation, and then enough branched oliogester of Example 9 is added to affect esterification of 25% of the branched oligoester's hydroxyl groups with the half-carboxylated linear oligoester. The stoichiometry is the same as in Example 11.

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11393~

To a 5-liter flask equipped as before are added 1800 g (1.30 moles) of linear oligoester 3, 193~2 g (1.30 moles) of _-phthalic anhydride and 40 g of xylene. The mixture is heated at 125C-150C for 1 hour at which point 1279 g (1.3 moles) of branched oligoester 3 are added.
The mixture is heated at 220C-270C until 23.4 y (1.30 moles) of water have been removed. The resin is diluted with 520 g of xylene to afford a polyester with the following physical properties:
Acid no. = 0.75 Theoretical OH no. = 90 Measured OH no. = 93 % weight solids = 85 Gardner-Holdt viscosity = Z6 at 25C
GPC molecular weight distribution:
Mn = 2400 Mw = 37,000 Mz = 208,000 d = 15.4 Tg = -36C
Comparative Test BATCH OR CONTINUOUS POLYMERIZATION
_ . _ : 25 This test showsbatch or continuous poly-esterification of the monomers present in the starting materials of Examples 11 and 12. The : stoichiometric balance of monomers is adjusted so as to match the amounts introduced from the :: . 30 branched and linear oligomers and the o-phthalic anhydride quite closely.
To a 5-liter flask equipped as before : : are added:

:

. :
.

~203~3~

650.10 y neopentyl glycol (6.25 moles) 202.5 g trimethylolpropane (1.5 moles) 207.5 g isophthalic acid (1.25 moles) 912.5 g a~elaic acid (4.85 moles) 111.36 g o~phthalic anhydride (0.75 moles) Xl = 4.17 X2 = 1.13 X3 = 0.41 The mixture is heated at 155C-270C
to distill 233.1 g (12.95 moles) of water. The resin is then diluted with 327 g of xylene to yield a polyester resin with the following properties:
Acid no. = 0.82 Theoretical OH no. = 90 Measured OH no. = 94 weight solids = 85 Gardner-Holdt viscosity = 25 at 25C
GPC molecular weight distribution:
Mn = 2100 ~lw = 19,000 Mz = 79,000 d = ~.05 Tg - -30C
It is important to note that the theoretical hydroxyl numbers of the polymers are the same between this test and Examples 11 and 12. However, Gardner-Holdt solution viscosity versus percent solids by weight behavior of the three polymers is very dif-ferent depending upon the mode of preparation, with the viscosity of~the batch test being higher for its molecular weights than would be expected from Examples 11 and 12 it they had produced materials of similar molecular~weight. The molecular weight distributions vary also depending upon the mode~of polymerization.
The changes in molecular weight distributions as . j ., .

. , .

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a function of polymerization process are dependent upon the chain length (or Mn) of the linear segment, holding the molecular weight of the branched component constant. With a Mn of the linear segment as low as Mn 400, the GPC distributions of all polymers and the viscosity/solids behavior prepared by staged or continuous processes are identical. The Mn of the linear segment needs to be at least about 500 for the advantages of the invention to become manifest.
Similar results are obtained with the staged polymerizations of the previous examples if polymerization catalysts such as dibutyl tin oxide are added in catalytic quantities.
COATING VARIATIONS

VARYING COMPOSITIONS IN COLOR COAT
Polyester/Melamine Ratio: 90/20 - 50/5 Pigment/Binder Ratio: 2/100 - 100/100 Melamine Variations:
Cymel** 1158 produced by American Cyanamid Resimene** 717 produced by Monsanto Resimene 735 produced by Monsanto Cymel 325 produced by American Cyanamid Resimene 747* and 755 produced by Monsanto *Requires 0.2-0.5~ strong acid to obtain acceptable cure and film properties at 250F X 30 minutes bakes.
Examples of strong acids:
p-toluene sulfonic acid dodecylbenzene sulfonic acid ; dinonylnaphthalene disulfonic acid phosphoric acid oxalic acid ** denotes trade mark ~3 a3~

VARYING COMPOSITIONS IN CLEAR COAT
Polyester lA/Polyester lB ratio and Polyester/Melamine ratio can be varied to accom-modate necessary properties for application over S flexible and/or rigid subs-trates.
Blends of various melamines are possible to accommodate cure requirements such as under-bake and overbake properties.

Example 13 FLEXIBLE POLYESTER COLOR COAT
Comeonent Weight (I % Binder Solids Staged Polyester Lo - Ex. 385.62 35 Staged Polyester LB - Ex. 485.62 35 15 Resimene 717 102.6 30 Tinuvin*328 from Ciba Geigy 6.84 2 Polymeric hindered amune light stabilizer 3.42 37.6 11 -Butyl alcohol Silicone oil flow enhancement 0.34 0.10 agent Ed silica 10.26 3 25 Alcoa 7575 34.2 10 Polyester/Melamine Ratio = 70/30 by weight Pigment/Bmder = 10/100 by weight : Thinned with a 70/30 by weight mixture of MæK/amylacetate : % weight solids at spray = 45 % volume solids at spray = 34 Spray viscosity - 20-25 seconds Fisher ~2 cup.

* denotes trade mark ~Z~ 3~g Example 14 FLEXIBLE POLYESTER CLEAR COAT
Component Weight % Binder Solids Staged Polyester lA - Ex. 3 164.70 35 Staged Polyester lB - Ex. 4 164.70 35 Resimene 717 146.3 30 Tinuvin 328 8.0 2 Polymeric hindered amine 4.0 light stabilizer 10 Silicone oil 0.6 0.15 Butyl Alcohol 60 15 Polyester/melamine Ratio = 70/30 Thinned with a 70/30 by weight mixture of amylacetate/xylene % weight solids = 53.5 at spray % valumn solids = 45.5 at spray Spray viscosity = 35 seconds #2 Fisher cup Example 15 RIGlD POLYESTER CLEAR COAT
-Component Weight (g) Binder Solids 20Staged Polyester lA - Ex. 3 706 60 Resimene 717 488 40 Tinuvin 328 20 2 Polymeric hindered amine 10 light stabilizer 25 Silicone oil 1 0.1 Butyl alcohol 150 15 Polyester/melamine Ratio = 60/40 Thinned with a 70/30 by weight mixture of amylacetate xylene % weight solids at spray =
% volume solids at spray = 48 Spray viscosity - 35 seconds #2 Fisher cup P~Z~393~

APPLICATION OF POLYESTER COLOR COAT/CLEAR
COAT SYSTEMS
_ Example 16 FLEXIBLE POLYESTER COLOR COAT/FLEXIBLE POLYESTER
CLEAR COAT
Coatings applied wet-on-wet on flexible reactive injection molded (RIM) substrate were tested with film builds (dry - after bake) of:
color coat = 0.5 mils and clear coat = 1.6 mils.
The baking schedule was 250F for 30 minutes Appearance 20 gloss = 89 60 gloss = 98 Distlnctness of image (DOI) 65 These measurements were made with a Garnder Instruments Glossmeter*and a Hunter*DOI Meter.
Tukon Hardness was 2.2 Knoop.
The -20F flexibility was measured by bending a 1" x 6" strip of coated substrate over a cold 1/2" cylindrical mandrel. Panel was cooled in a -20F deep freezer along with the mandrel for 4 hours. Flexibility test showed no crac]cing of the coating.
A crosshatch adhesion test showed no loss of adhesion.
Toughness was measured by attempting to cause cohesive adhesion failure by marring film with a knife held perpendicular to the film and dragged across it. It was difficult to mar the film with the knife.

::
35 * denotes trade mark ~3~3~

Exposure for 96 hours in a condensing humidity cabinet set at 100F and 100% relative humidity showed no gloss loss or discloration of the coating and no loss of adhesion or toughness.
Excellent chip resistance after chilling to -10F
for 4 hours was obtained in a standard Gravelometer test.
There was no film distortion or softening after 200 repeated double rubs with methyl ethyl ketone, and there was no distortion or softening after allowing 3 drops of xylene to evaporate from a test sample.
In accelerated weathering tests for 1530 hours exposure to quartz lamp ultraviolet light, there was 70~ retention of 20 gloss reflectance and no loss of room temperature flexibility.
Example 17 FLEXIBLE POLYESTER COLOR COAT/RIGID POLYESTER
CLEAR COAT
I.
Wet on-wet coatings applied on reinforced rim (RRIM) and sheèt molded compound (SMC) were tested with film builds (dry-after bake) of: color coat = 0.6 mils and clear coat = 1.6 mils. The 25 baking schedule was 250F for 30 minutes.
Appearance RRIM: 20 gloss = 90 60 gloss = 93 DOI = 60 SMC: 20 gloss = 92 60 gloss = 99 DOI = 64 The Tukon Hardness on SMC was 7.7 Knoop.
The 0F flexibility over RRIM was measured by bending a 4" x 12" coated panel to a 90 angle over a cold 1" cylindrical mandrel. Both 3~39 the coated panel and the mandrel are chilled in a 0F freezer for 4 hours. No cxacking of the coating was no-ted.
A crosshatch adhesion -test showed no loss of adhesion on both RRIM and SMC substrates.
Toughness on RRIM and on SMC was measured by attempting to mar film by dragging a U.S. 10-cent coin across the coating while holding the dime at a 45 angle to the plane of the substrate. It was difficult to mar the film with the coin over both substrates.
Exposure for 96 hours in a condensing humidity cabinet set at 100F and 100~ relative humidity showed no gloss loss or discoloration of the coating and no loss of adhesion or toughness over both RRIM and SMC.
On both substrates, excellent chip resistance after chilling to -10F for 4 hours was obtained in a standard Gravelometer test.
There was no film distortion or softening after 200 repeated double rubs with methyl ethyl ketone over both RRIM and SMC, and there was no distortion or softening after allowing 3 drops of xylene to evaporate from test samples on both 2 5 RRIM and SMC.

. !

Claims (12)

CLAIMS:
1. A non-equilibrium, two-stage polymeri-zation process conducted without external catalysts for producing polyester copolymers having a linear segment with terminal hydroxyl groups and a number average molecular weight (Mn) of at least about 500 and a branched segment with lateral hydroxyl groups characterized in that in the first stage of the process one half of the carboxyl groups of a diacid or a acid di-anhydride are reacted in approximately stoichiometric proportions with one of (A) one half of the hydroxyl groups of the linear segment and (B) 10-80% of the hydroxyl groups of the branched segment to form a first reaction product, and then in the second stage of the process the other half of the carboxyl groups of the first reaction product are reacted in approximately stoichiometric proportions with the hydroxyl group of the other of (A) and (B).
2. The process of claim 1 wherein the reaction of the first stage is conducted at temperatures of at least about 100°C and the reaction of the second stage is conducted at temperatures of at least about 200°C.
3. The process of claim 1 wherein in the first stage said carboxyl groups are reacted with the hydroxyl groups of the branched segment.
4. The process of claim 1 wherein in the first stage said carboxyl groups are reacted with the hydroxyl groups of the linear segment.
5. A polyester copolymer produced by the process of claim 1.
6. polyester copolymer produced by the process of claim 2.
7. A polyester copolymer produced by the process of claim 3.
8. A polyester copolymer produced by the process of claim 4.
9. A polyester copolymer of claim 6 wherein after the first stage and before the second stage of polymerization the branched segment has a number average molecular weight of 750-1000, a hydroxyl number of 175-300, an acid number of 20-60, and a number average functionality of 2.5-11; and the linear segment has a number average molecular weight of 500-3000, a hydroxyl number of 15-300, an acid number of less than 5 and a number average functionality of 1.1-2.
10. A polyester copolymer of claim 7 wherein after the first stage and before the second stage of polymerization the branched segment has a number average molecular weight of 750-1000, a hydroxyl number of 175-300, an acid number of less than 5, and a number average functionality of 2.5-11; and the linear segment has a number average molecular weight of 500-3000, a hydroxyl number of 15-300, an acid number of 20-60 and a number average functionality of 1.1-2.
11. A coating composition comprising A. a polyester copolymer of claim 9, and B. 10-50% by weight based on A plus B
of a crosslinker selected from melamine/formaldehyde resins, di- and poly-isocyanate resins, and urea formaldehyde resins.
12. A coating composition comprising A. a polyester copolymer of claim 10, and B. 10-50% by weight based on A plus B of a crosslinker selected from melamine/formaldehyde resins, di- and poly-isocyanate resins, and urea formaldehyde resin.
CA000443207A 1982-12-15 1983-12-13 Staged copolymerization of polyesters Expired CA1203939A (en)

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US450,135 1982-12-15

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JP (1) JPS59117527A (en)
AT (1) AT29507T (en)
AU (1) AU560895B2 (en)
BR (1) BR8306792A (en)
CA (1) CA1203939A (en)
DE (1) DE3373484D1 (en)
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US4659780A (en) * 1985-03-18 1987-04-21 E. I. Du Pont De Nemours And Company Acrylourethane reaction product
US4632964A (en) * 1985-03-28 1986-12-30 E. I. Du Pont De Nemours And Company Flexible finishes from branched aliphatic polyester urethanes and a melamine crosslinker
GB8609034D0 (en) * 1986-04-14 1986-05-21 Ucb Sa Preparation of polyesters
US4740426A (en) * 1986-08-29 1988-04-26 E. I. Du Pont De Nemours And Company Conductive primer composition
CA1320779C (en) * 1986-08-29 1993-07-27 Henry Stever Tremper Iii Conductive primer composition
US5068063A (en) * 1989-12-28 1991-11-26 E. I. Du Pont De Nemours And Company Non-carbon black containing conductive coating composition
US6413588B1 (en) * 1999-01-11 2002-07-02 E. I. Du Pont De Nemours And Company Method of producing durable layered coatings
US6689457B1 (en) 1999-04-14 2004-02-10 E. I. Du Pont De Nemours And Company Electrically conductive coatings applied by internally charged electrostatic sprayers
TWI238214B (en) * 2001-11-16 2005-08-21 Du Pont Method of producing micropulp and micropulp made therefrom
TWI228553B (en) * 2001-11-16 2005-03-01 Du Pont Method of producing coating compositions and coating compositions made therefrom
US7402624B2 (en) * 2004-11-08 2008-07-22 E.I. Du Pont De Nemours & Company Graft copolymers with segmented arms and their preparation and use
US8586701B2 (en) * 2005-10-28 2013-11-19 Eastman Chemical Company Process for the preparation of copolyesters based on 2,2,4,4-tetramethyl-1,3-cyclobutanediol and 1,4-cyclohexanedimethanol
CN101395306B (en) * 2006-03-01 2012-02-15 宝洁公司 Fibers formed of ester condensates and process for forming fibers from ester condensates
US7211634B1 (en) * 2006-04-28 2007-05-01 Eastman Chemical Company Process for the preparation of polyesters containing 1,4-cyclohexanedimethanol
CA2705870A1 (en) * 2007-11-21 2009-06-04 Eastman Chemical Company Plastic baby bottles, other blow molded articles, and processes for their manufacture
US20090281230A1 (en) * 2008-05-09 2009-11-12 Ashland Licensing And Intellectual Property Llc Branched low profile additives and methods of production

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FR1443401A (en) * 1965-05-12 1966-06-24 Alsthom Cgee Mixed polyesters of aromatic acids esterified by aromatic polyols and aliphatic polyols, having a regular block structure in each of the repeating units
US3449467A (en) * 1965-06-03 1969-06-10 Union Carbide Corp Hydroxyl terminated polyester oligomers
US3496220A (en) * 1966-04-04 1970-02-17 Mobil Oil Corp Esterification process
US3704255A (en) * 1971-03-03 1972-11-28 Du Pont Polyesters
JPS4927091A (en) * 1972-07-08 1974-03-11
FR2295990B1 (en) * 1974-12-24 1979-02-23 Rhone Poulenc Ind
US4275189A (en) * 1980-02-28 1981-06-23 Cargill, Incorporated Neopentyl glycol, terephthalate, dicarboxy acid, trimellitate thermosetting resin

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EP0112250A2 (en) 1984-06-27
EP0112250A3 (en) 1985-06-19
ZA8309292B (en) 1985-07-31
ES527987A0 (en) 1985-11-01
AU560895B2 (en) 1987-04-16
AT29507T (en) 1987-09-15
ES527987D0 (en)
JPS59117527A (en) 1984-07-06
CA1203939A1 (en)
US4442269A (en) 1984-04-10
ES8601260A1 (en) 1985-11-01
BR8306792A (en) 1984-07-17
EP0112250B1 (en) 1987-09-09
DE3373484D1 (en) 1987-10-15
AU2231383A (en) 1984-06-21

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